Mechanical modulation for multiplex gas chromatographic analyses at subatmospheric pressures.
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Lake Hoare (77 degrees 38' S, 162 degrees 53' E) is a perennially ice-covered lake at the eastern end of Taylor Valley in southern Victoria Land, Antarctica. The environment of this lake is controlled by the relatively thick ice cover (3-5 m) which eliminates wind generated currents, restricts gas exchange and sediment deposition, and reduces light penetration. The ice cover is in turn largely controlled by the extreme seasonality of Antarctica and local climate. Lake Hoare and other dry valley lakes may be sensitive indicators of short term (< 100 yr) climatic and/or anthropogenic changes in the dry valleys since the onset of intensive exploration over 30 years ago. The time constants for turnover of the water column and lake ice are 50 and 10 years, respectively. The turnover time for atmospheric gases in the lake is 30-60 years. Therefore, the lake environment responds to changes on a 10-100 year timescale. Because the ice cover has a controlling influence on the lake (e.g. light penetration, gas content of water, and sediment deposition), it is probable that small changes in ice ablation, sediment loading on the ice cover, or glacial meltwater (or groundwater) inflow will affect ice cover dynamics and will have a major impact on the lake environment and biota.
Two major questions have been raised by prior explorations of Mars. Has there ever been abundant water on Mars? Why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface? The work reported here describes a model soil system of Mars Soil Analog Materials, MarSAM, with attributes which could help resolve both of these dilemmas. The first set of MarSAM consisted of a suite of variably iron/calcium-exchanged montmorillonite clays. Several properties, including chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, of these clays have been examined. Also, simulations of the Viking Labeled Release Experiment using the MarSAM were performed. The results of these studies show that surface iron and adsorbed water are important determinants of clay behavior as evidenced by changes in reflectance, water absorption, and clay surface reactions. Thus, these materials provide a model soil system which reasonably satisfies the constraints imposed by the Viking analyses and remote spectral observations of the Martian surface, and which offers a sink for significant amounts of water. Finally, our initial results may provide insights into the mechanisms of reactions that occur on clay surfaces as well as a more specific approach to determining the mineralogy of Martian soils.
Based upon arguments concerning properties of the environment and the energetics of nitrogen transformation reactions, new hypotheses regarding their evolution are presented. These hypotheses are supported by new calculations and observations germane to understanding the evolution of the nitrogen cycle. From calculations of shock production by meteor impact, we suggest that impact produced fixed nitrogen could have resulted in the entire reservoir of Earth's N2 being converted into fixed nitrogen at the end of accretion. We have significantly improved upon previous calculations of the abiotic fixation rate on the early earth and find a rate of fixation by lightning of approximately 1-3 x 10(16) molecules NO/J, which is 2 to 3 times greater than previous estimates. This strengthens the suggestion, corroborated by the predominance of a single nitrogenase enzyme, that biological nitrogen fixation may have been a late evolutionary development, after the development of an aerobic atmosphere. In addition, we show for the first time that HNO, predicted to be the main product of atmospheric photochemical reactions involving NO on the primitive Earth by photochemical models, would eventually become NO2- and NO3- after reaching the Earth's surface. Based upon microbe-environment interactions on an ecological as well as a biochemical scale we suggest that denitrification arose prior to aerobic respiration and that nitrification arose after the advent of an aerobic atmosphere. We hypothesize the following evolutionary sequence for the biological transformation of nitrogen compounds: Ammonification --> Denitrification --> Nitrification --> Nitrogen fixation.
The early atmosphere of the Earth is considered to have been reducing (H2 rich) or neutral (CO2-N2). The present atmosphere by contrast is highly oxidizing (20% O2). The source of this oxygen is generally agreed to have been oxygenic photosynthesis, whereby organisms use water as the electron donor in the production of organic matter, liberating oxygen into the atmosphere. A major question in the evolution of life is how oxygenic photosynthesis could have evolved under anoxic conditions--and also when this capability evolved. It seems unlikely that water would be employed as the electron donor in anoxic environments that were rich in reducing agents such as ferrous or sulfide ions which could play that role. The abiotic production of atmospheric oxidants could have provided a mechanism by which locally oxidizing conditions were sustained within spatially confined habitats thus removing the available reductants and forcing photosynthetic organisms to utilize water as the electron donor. We suggest that atmospheric H2O2 played the key role in inducing oxygenic photosynthesis because as peroxide increased in a local environment, organisms would not only be faced with a loss of reductant, but they would also be pressed to develop the biochemical apparatus (e.g., catalase) that would ultimately be needed to protect against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis while global conditions were still anaerobic.
In the traditional concept for the origin of life as proposed by Oparin and Haldane in the 1920s, prebiotic reactants became slowly concentrated in the primordial oceans and life evolved slowly from a series of highly protracted chemical reactions during the first billion years of Earth's history. However, chemical evolution may not have occurred continuously because planetesimals and asteroids impacted the Earth many times during the first billion years, may have sterilized the Earth, and required the process to start over. A rapid process of chemical evolution may have been required in order that life appeared at or before 3.5 billion years ago. Thus, a setting favoring rapid chemical evolution may be required. A chemical evolution hypothesis set forth by Woese in 1979 accomplished prebiotic reactions rapidly in droplets in giant atmospheric reflux columns. However, in 1985 Scherer raised a number of objections to Woese's hypothesis and concluded that it was not valid. We propose a mechanism for prebiotic chemistry in clouds that satisfies Scherer's concerns regarding the Woese hypothesis and includes advantageous droplet chemistry. Prebiotic reactants were supplied to the atmosphere by comets, meteorites, and interplanetary dust or synthesized in the atmosphere from simple compounds using energy sources such as ultraviolet light, corona discharge, or lightning. These prebiotic monomers would have first encountered moisture in cloud drops and precipitation. We propose that rapid prebiotic chemical evolution was facilitated on the primordial Earth by cycles of condensation and evaporation of cloud drops containing clay condensation nuclei and nonvolatile monomers. For example, amino acids supplied by , or synthesized during entry of, meteorites, comets, and interplanetary dust would have been scavenged by cloud drops containing clay condensation nuclei. Polymerization would have occurred within cloud systems during cycles of condensation, freezing, melting, and evaporation of cloud drops. We suggest that polymerization reactions occurred in the atmosphere as in the Woese hypothesis, but life originated in the ocean as in the Oparin-Haldane hypothesis. The rapidity with which chemical evolution could have occurred within clouds accommodates the time constraints suggested by recent astrophysical theories.
The thick sequences of layered deposits found in the Valles Marineris have recently been determined by S.S. Nedell, S.W. Squyres, and D.W. Andersen (1987, Icarus, 70, 409-441) to contain a minimum of approximately 10(5) km3 of material. We suggest that this material could be derived from the precipitation of 30 mbar of atmospheric CO2 as carbonates in lakes. As surface temperatures fell on Mars, the presence of an insulating ice cover would have allowed liquid water to exist, fed by transitory surface melting. Atmospheric CO2 would have accumulated in such lakes enhancing carbonate precipitation. Support for this hypothesis comes from processes that occur in the perennially frozen lakes in the dry valleys of Antarctica where the mean temperature is 253 degrees K and the lake water is supersaturated with atmospheric gases. A search of the recently reissued Mariner 6/7 infrared spectrometer data in the wavelength region between 2 and 6 micrometers failed to confirm the presence of carbonates. Due to the fact that no spectral footprints appear to directly overlie the layered deposits, and that deposits may be blanketed by an eolian mantle, this negative result is inconclusive. We feel that the canyon deposits are still a prime site for future searches for carbonates on Mars.
Detailed models of the internal structures of Pluto and Charon, assuming rock and water ice as the only constituents, indicate that the mean silicate mass fraction of this two-body system is on the order of 0.7; thus the Pluto/Charon system is significantly "rockier" than the satellites of the giant planets (silicate mass fraction approximately 0.55). This compositional contrast reflects different formation mechanisms: it is likely that Pluto and Charon formed directly from the solar nebula, while the circumplanetary nebulae that produced the giant planet satellites were derived from envelopes that surrounded the forming giant planets (envelopes in which icy planetesimals dissolved more readily than rocky planetesimals). Simple cosmic abundance calculations, and the assumption that the Pluto/Charon system formed directly from solar nebula condensates, strongly suggest that the majority of the carbon in the outer solar nebula was in the form of carbon monoxide; these results are consistent with (1) inheritance from the dense molecular clouds in the interstellar medium (where CH4/CO < 10(-2) in the gas phase) and/or (2) of the Lewis and Prinn kinetic inhibition model of solar nebula chemistry. Theoretical predictions of the C/H enhancements in the atmospheres of the giant planets, when compared to the actual observed enhancements, suggest that 10%, or slightly more, of the carbon in the outer solar nebula was in the form of condensed materials (although the amount of condensed C may have dropped slightly with increasing heliocentric distance). Strict compositional limits computed for the Pluto/Charon system using the densities of CH4 and CO ices indicate that these pure ices are at best minor components in the interiors of these bodies, and imply that CH4 and CO ices were not the dominant C-bearing solids in the outer nebula. Clathrate-hydrates could not have appropriated enough CH4 or CO to be the major form of condensed carbon, although such clathrates may be necessary to explain the presence of methane on Pluto after its formation from a CO-rich nebula. Laboratory studies of carbonaceous chondrites, and spacecraft observations of Comet Halley, strongly suggest that of the remaining possibilities, organic material, rather than elemental carbon, is the most likely candidate for the dominant C-bearing solid in the outer solar nebula. We conclude that the majority of the carbon in the outer solar nebula was in gaseous CO; 10% to a few tens of percent of the C was in condensed organic materials; and at least a trace amount of carbon was in methane gas.
We have developed a radiative-convective model of the thermal structure of Titan's atmosphere. The model computes the solar and infrared radiation in a series of spectral intervals with vertical resolution. Sources of opacity in the visible and near infrared include stratospheric haze particles, methane cloud particles, and gaseous methane; sources of opacity in the thermal infrared include the pressure-induced opacity of N2, CH4, and H2, the permitted transitions of C2H2 and C2H6, and particulate opacity. The haze properties are determined with a simple microphysics model. The model contains a minimum of free parameters and we try to determine these by fits to independent data sets. We find that gas and haze opacity alone, with the temperatures fixed by Voyager observations, produces a model that is within a few percent of radiative convective balance everywhere in the atmosphere. In a self-consistent computation of temperatures, we find that our model calculation for the surface temperature is, in general, colder than the observed value by 5-10 degrees K. The presence or absence of methane condensation clouds only slightly alters the results. Good agreement can be obtained by adjusting the parameters in the model. The model parameters in these optimized cases are typically within 15% of the baseline values and within the limits allowed by observations. We conclude that the most important factors controlling Titan's thermal structure are absorption of sunlight by the stratospheric haze and the pressure-induced gas opacity in the infrared. Within the uncertainties of the model, these effects can explain the observed temperature profile. Condensation clouds play a minor role, if any.
The prospect of life on Mars today is daunting. Especially problematic for a potential life form is a lack of water, particularly in a liquid state; extremely cold temperatures; ultraviolet and ionizing radiation; and soil oxidants. Yet, "oases" where life might persist have been suggested to occur in rocks (in analogy with endolithic microorganisms described from deserts around the world), in polar ice caps (in analogy with snow and ice algae) and in possible volcanic regions (in analogy with chemoautotrophs living in deep sea hydrothermal vents); all are critically examined. Microorganisms are known to be able to survive in salt crystals, and recently it has been shown that organisms can metabolize while encrusted in evaporites. Because evaporites are thought to occur on Mars and can attenuate light in the UV range while being far more transparent to radiation useful for photosynthesis (400-700 nm), and because of the properties of these "endoevaporitic" organisms, I propose that such communities provide a new model system for studying potential life on Mars. On the basis of this model, I suggest possibilities for site selection for future exobiological experiments on Mars.
We report on new observations of Titan with the International Ultraviolet Explorer in the mid-UV range (lambda approximately 220-335 nm). We use these data to determine upper limits for the abundances of simple organic compounds in the gas phase and to further constrain the properties of the high altitude haze on Titan. As a baseline, we adopted the parametrized microphysical model of McKay et al. (1989) which is successful at reproducing Titan's thermal structure while satisfying several other observational constraints in the visible and IR regions. However, we find that such a model--in which all particles at a given altitude are assumed to have the same size--cannot match simultaneously the IUE observations and the visible/IR data, even when allowance is made for a wide range of values in the adjustable parameters. On the other hand, a good overall agreement is obtained when considering a biomodal size distribution, with small haze particles or "polymers" (r < 0.02 micrometer) acting as strong Rayleigh absorbers below 300 nm and larger haze particles (r approximately 0.1-0.5 micrometer) being responsible for the characteristics of the albedo spectrum in the near-UV, visible, and IR regions. This approach is consistent with the results of several previous investigations of the properties of Titan's haze, although our preferred vertical structure for the haze + polymer material somewhat differs from earlier solutions. On the basis of simple dynamical considerations, we adopted a uniformly mixed layer between 150 and 600 km. The IUE data allow us to place fairly stringent constraints on the abundance of the Rayleigh absorbers, if we assume that their optical properties are similar to those of laboratory-synthesized "tholins": The column-mass density of this material--the essential observable that can be determined from our study--is of the order of 5 micrograms cm-2. This would correspond to number-densities between 10(3) and 10(7) cm-3 in the 150-600 km altitude range, if the average particle radius is between 0.001 and 0.02 micrometer. Such high number densities are a priori at odds with the estimated coagulation lifetime for particles of that size. Thus, our proposed bimodal size distribution is plausible only if inhibiting processes act to slow down considerably the coagulation of polymers in Titan's stratosphere.
Microphysical simulations of Titan's stratospheric haze show that aerosol microphysics is linked to organized dynamical processes. The detached haze layer may be a manifestation of 1 cm sec-1 vertical velocities at altitudes above 300 km. The hemispherical asymmetry in the visible albedo may be caused by 0.05 cm sec-1 vertical velocities at altitudes of 150 to 200 km, we predict contrast reversal beyond 0.6 micrometer. Tomasko and Smith's (1982, Icarus 51, 65-95) model, in which a layer of large particles above 220 km altitude is responsible for the high forward scattering observed by Rages and Pollack (1983, Icarus 55, 50-62), is a natural outcome of the detached haze layer being produced by rising motions if aerosol mass production occurs primarily below the detached haze layer. The aerosol's electrical charge is critical for the particle size and optical depth of the haze. The geometric albedo, particularly in the ultraviolet and near infrared, requires that the particle size be near 0.15 micrometer down to altitudes below 100 km, which is consistent with polarization observations (Tomasko and Smith 1982, West and Smith 1991, Icarus 90, 330-333). Above about 400 km and below about 150 km Yung et al.'s (1984, Astrophys. J. Suppl. Ser. 55, 465-506) diffusion coefficients are too small. Dynamical processes control the haze particles below about 150 km. The relatively large eddy diffusion coefficients in the lower stratosphere result in a vertically extensive region with nonuniform mixing ratios of condensable gases, so that most hydrocarbons may condense very near the tropopause rather than tens of kilometers above it. The optical depths of hydrocarbon clouds are probably less than one, requiring that abundant gases such as ethane condense on a subset of the haze particles to create relatively large, rapidly removed particles. The wavelength dependence of the optical radius is calculated for use in analyzing observations of the geometric albedo. The lower atmosphere and surface should be visible outside of regions of methane absorption in the near infrared. Limb scans at 2.0 micrometers wavelength should be possible down to about 75 km altitude.
From February to March 1989 the Phobos 2 spacecraft took 37 TV images of Phobos at a distance of 190-1100 km. These images complement Mariner-9 and Viking data by providing higher-resolution coverage of a large region West of the crater Stickney (40-160 degrees W) and by providing disk-resolved measurements of surface brightness at a greater range of wavelengths and additional phase angles. These images have supported updated mapping and characterization of large craters and grooves, and have provided additional observations of craters' and grooves' bright rims. Variations in surface visible/near-infrared color ratio of almost a factor of 2 have been recognized; these variations appear to be associated with the ejecta of specific large impact craters. Updated determinations of satellite mass and volume allow calculation of a more accurate value of bulk density, 1.90 +/- 0.1 g cm-3. This is significantly lower than the density of meteoritic analogs to Phobos' surface, suggesting a porous interior perhaps containing interstitial ice.
It has been suggested that slope fluctuations on the scale of pixel dimensions could be determined by statistical photoclinometry. A closer study of the surface of Phobos reveals variations in the scattering properties of single particles and micro-structures formed by the particles. In the present context, the photoclinometric method of brightness moments is extended to account for these variations by allowing statistical fluctuations in the phase function of the assumed Lommel-Seeliger scattering law. The mean slope on the investigated regions of Phobos has been found to vary from approximately 12 degrees on a 61m scale to approximately 7 degrees on a 216-272m scale. On the same scales, a value of the order of 2% has been obtained for the standard deviation of the scattering phase function. Hints of a fractal-like scale-invariance have been noticed in the covariance function of brightness.
Analysis of disk resolved images of Phobos obtained by the Phobos 2 spacecraft allows us to study the surface scattering law and albedo variations. From low phase angle images we find variations in local geometric albedo approximately 10%, with a correlation length approximately 1km. The scattering law is reasonably well matched by the recent proposed LPI (Lumme et al. 1990a) model, which allows us to deduce a small scale (approximately 1 mm) surface roughness (approximately 0.5), defined here as the rms. tangent of the local surface normal relative to the mean surface normal in the Duxbury (1991) model of Phobos. This value is very close to what has been found for Mercury and the Moon.
Among the major objectives of NASA's program of space exploration is a better understanding of the origin and evolution of the solar system. Crucial to this objective is the study of comets, which are thought to be the most primitive, pristine bodies remaining in the solar system. The importance of the study of comets has led NASA to plan a mission to rendezvous with comet Tempel 2 in 1997. Critical to the understanding of comets will be measurements of the nucleus material to determine its elemental and isotopic composition, its mechanical properties, and its thermal state and properties. This paper describes a proposal for a Comet Nucleus Penetrator to accomplish these measurement goals. The Comet Nucleus Penetrator will implant instruments into the comet's nucleus beneath a probable volatile-depleted surface mantle into material more representative of the bulk composition of the nucleus.
The comparability of the early environments of Mars and Earth, and the biological evolution which occurred on early earth, motivates serious consideration of the possibility of an early martian biota. Environments which could have contained this early martian life and which may presently contain evidence of this former life include aquatic, ice, soil, and rock habitats. Several analogs of these potential early martian environments, which can provide useful information in searching for extinct life on Mars, are currently available for study on Earth. These terrestrial analogs include the perennially ice-covered lakes and sandstone rocks in the Polar Deserts of Antarctica, surface of snowfields and glaciers, desert soils, geothermal springs, and deep subsurface environments.